A multiplicity of process to obtain boron compounds are well known in the art, particularly boric acid, from minerals containing boron such as colemanite and/or howlite minerals, as well as other minerals containing borax, among which that described by Taylor, U.S. Pat. No. 2,746,841, granted to Borax Consolidated, Ltd. and issued on May 22, of 1956, can be mentioned. In that process a mineral containing insoluble minerals and borax (Na2B4O7.10H2O) together a mother liquid obtained from the process for dissolving borax are introduced in a dissolving tank; and the borate solution is separated from the insoluble fraction of the mineral in order to take the clear solution to a sulfate reactor. The solution is treated with sulfuric acid so as to convert all of the sodium oxide in the solution to sodium sulfate, thus producing an acid solution containing, primarily, sodium sulfate and boric acid. The acidified solution is heated so that the concentration of sodium sulfate exceeds the solubility of normal saturation at the existing temperature in order to precipitate anhydrous sodium sulfate. The precipitate is separated from the solution and washed so that it can be sold as pure sodium sulfate. The remaining solution, saturated with sodium sulfate and containing boric acid in elevated concentrations but not reaching to saturation, is cooled or is concentrated and then cooled; this increases the solubility of the sulfate and boric acid is precipitated which is crystallized from the cooled solution. The resulting crystals are separated from the solution and the boric acid thus crystallized is obtained as a product of the process. The remaining solution, which still contains sodium sulfate and boric acid in sufficiently high amounts to produce saturation, is returned as mother liquid to the mineral dissolving tank so that the dissolution stage can take place.
Another process known for the obtainment of boric acid is that one described and claimed by Dwyer in the U.S. Pat. No. 3,103,412 issued Sept. 10, 1963, assigned to Tholand, Inc. In that method treats minerals containing calcium borate, such as colemanite and howlite, are treated to recover useful boron compounds from said minerals. The process comprising: mixing the mineral with aqueous ammonium sulfate; heating the mixture to produce an ammonium pentaborate mud, precipitated calcium sulfate and gangue; filtering the mud to separate calcium sulfate and the gangue; cooling the filtrate in order to crystallizing the ammonium pentaborate; separating the crystalline pentaborate and reacting it with sulfuric acid in order to form boric acid and ammonium sulfate. Said boric acid is recovered as a reaction product and the ammonium sulfate solution thus formed is used to treat additional amounts of the mineral.
Still another process to obtain boric acid from colemanite is one described by Mathis, Pierre (Solvay et Cie.) German Publication No. 2,020,570, dated Nov. 12, 1970, in which boric acid is prepared through the decomposition of crude or calcined colemanite with CO2 at a pressure higher than atmospheric pressure and at moderate temperatures in the presence of water to separate the solid phase from the liquid phase, and crystallize the boric acid from said liquid phase.
Another process to obtain boric acid through the decomposition of colemanite is described by Bozadzhiev, P. (Bulgarian), God Vissh Khim-Tekhnol Inst. Sofia, 1973, 21 (2), 79-84 which comprises: producing boric acid by decomposition of the colemanite with monocalcium phosphate and double superphosphate. Decomposition percentages of 99.9% have been reported with said monocalcium phosphate and 98.1% with the double superphosphate.
Another process for the decomposition of colemanite is that one described by Bozadzhiev. P. (Bulgarian) God, Vissh Khim-Tekhnol Inst. Sofia. 1973 21 (2), 67-77 in which the colemanite is discomposed in the presence of an excess of phosphoric acid, through the reaction of colemanite with 15% phosphoric acid with which a practically quantitative decomposition within 60 minutes at a low temperature or 20 minutes at a higher temperature is achieved. The velocity of decomposition is controlled by diffusion so that a layer of the diffusion virtually consists of pure boric acid while starting from colemanite, monocalcium phosphate is formed.
Another process to obtain boric acid starting from minerals containing calcium, sodium and boron, such as ulexite, is described by Werner Janik et al in the Polish Pat. No. 218, 576, issued Sept. 26, 1979 appearing in German publication No. 3,029,349, issued Apr. 16, 1981. It includes the manufacture of boric acid from Peruvian ulexite by heating said ulexite in 96% sulfuric acid in an amount sufficient to precipitate calcium sulfate, resulting a suspension of calcium sulfate in a solution of boric acid plus other secondary products. The calcium sulfate is separated from the solution and is then treated with ion exchange apparatus in order to obtain the boric acid by acidification, crystallization and purification.
Finally, another process is known to obtain boric acid from minerals such as Kernite. This method is described by Miroslav Novak in the Czechoslovakian Pat. No. 184,560, dated Feb. 15, 1981. With this method, 74 to 83% of the total B2O3 contained in the kernite mineral or in the borax is recuperated through the decomposition of such minerals with diluted nitric acid at a relatively elevated temperature and the separation of the crude boric acid from the cooled solution. The mother liquors are concentrated to produce additional boric acid and the residual liquid phase is evaporated to give a fertilizer containing sodium nitrate and boric acid.
However all of the process described above and others of the previous art, require to be carried out the use of a starting material i.e., of a mineral of a high grade or quality and of low degree of contamination, particularly of a low arsenic, iron and aluminum contamination since, otherwise, the resulting products would be contaminated by the stated impurities.
There are large amounts of colemanite and howlite mineral deposits of a low grade or quality and which are highly contaminated. Man has searched a long time for a way to exploit the stated deposits even though to date it has not been possible in view of the fact that all of the existing process in the previous art were unable to benefice the stated minerals with reasonable efficiency. Therefore, for a long time economic and efficient process have been searched for in order to benefice this type of minerals of low grade and high degree of contamination.
Even though numerous investigations have been carried out in order to exploit the stated minerals whether by the concentration or the beneficiating methods, including the elimination of arsenic, iron and sulfate in order to obtain a boric acid useful for the glass industry, the procedures that have been tried to date using this particular method have not been entirely satisfactory. Such process have included mechanical methods, such as mill, attrition, flotation, etc., as well as chemical methods, such as the process of lixiviation, extraction by solvents or calcination. But even with all the processes that have been tried up to now, it has been found that a mineral is produced which is more or less concentrated and beneficiated with an average yield rate of 38 to 48% of B2O3 and with a relatively high recuperation rate of from 68 to 74%. These processes have not been sufficiently economical to try on an industrial scale, and they are incapable of adequately eliminating the arsenic, iron and aluminum contaminates contained in the minerals.